CN115677671A - Quinoxaline derivative and application thereof - Google Patents

Quinoxaline derivative and application thereof Download PDF

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CN115677671A
CN115677671A CN202211299144.2A CN202211299144A CN115677671A CN 115677671 A CN115677671 A CN 115677671A CN 202211299144 A CN202211299144 A CN 202211299144A CN 115677671 A CN115677671 A CN 115677671A
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曹建华
张海威
郭文龙
李程辉
王振宇
唐伟
刘赛赛
徐先锋
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Beijing Bayi Space LCD Technology Co Ltd
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Abstract

The invention relates to the technical field of organic electroluminescent materials, in particular to a quinoxaline derivative and application thereof. The structural formula of the quinoxaline derivative is shown as a formula (I); the compound shown in the formula (I) has a quinoxaline structure. The compound is applied to an organic electroluminescent element, so that the driving voltage can be obviously reduced, the luminous efficiency can be improved, and the service life can be prolonged.
Figure DDA0003901831170000011

Description

Quinoxaline derivative and application thereof
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a quinoxaline derivative and application thereof in an organic light-emitting element.
Background
In general, the organic light emitting phenomenon refers to a phenomenon in which light is emitted when electric energy is applied to an organic substance; that is, when an organic layer is disposed between an anode and a cathode, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer; when the injected holes and electrons meet, excitons are formed, and when the excitons transition to a ground state, light and heat are emitted.
In recent years, organic electroluminescent display technology has become mature, some products have entered the market, but in the process of industrialization, many problems still need to be solved. In particular, various organic materials used for manufacturing elements have many problems which are not solved, such as carrier injection and transmission performance, electroluminescent performance of the materials, service life, color purity, matching between various materials and between various electrodes, and the like; especially, the luminous efficiency and the service life of the light-emitting element are not practical, which greatly limits the development of the OLED technology. The metal complex phosphorescent material utilizing triplet state luminescence has high luminescence efficiency, and green and red materials of the metal complex phosphorescent material meet the use requirements, but the metal complex phosphorescent material requires a phosphorescent material or a hole material with a high triplet state energy level to be matched with the metal complex phosphorescent material, so that the development of the phosphorescent material or the hole material with the high triplet state energy level is an urgent need of the current development of the OLED.
Under the current technological development, improvements are also needed, both for fluorescent materials and for phosphorescent materials, in particular in terms of operating voltage, efficiency and lifetime for use in organic electroluminescent elements and thermal stability during sublimation.
Accordingly, in order to overcome the above-described problems of the conventional techniques and further improve the characteristics of the organic electroluminescent element, development of a more stable and effective substance which can be used as a phosphorescent material or a hole-forming material in the organic electroluminescent element is continuously required.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a quinoxaline derivative, which can improve the thermal stability of materials and the capability of transporting carriers, and an organic electroluminescent element prepared by utilizing the quinoxaline derivative can obviously reduce the driving voltage, improve the luminous efficiency and prolong the service life; another object of the present invention is to provide the use of the compound.
Specifically, the invention provides the following technical scheme:
the invention provides a quinoxaline derivative, the structural formula of which is shown as the formula (I):
Figure BDA0003901831150000011
wherein,
L 1 selected from the group consisting of single bonds, substituted or unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 Heteroarylene group;
X 1 、x 2 each independently is CR 3 Or X 1 And X 2 Represents a group of formula (II) or (III);
Figure BDA0003901831150000021
a represents, identically or differently on each occurrence, CR 4 Or N, and "^" indicates the adjacent group X in formula (I) 1 And X 2 (ii) a And in X 1 And X 2 When is of the formula (II), R 1 、R 2 Is not hydrogen or phenyl;
g represents O, S or NR 5 ；
R 1 、R 2 The same or different is selected from hydrogen or R 1 And R 2 Joined or fused to form a substituted or unsubstituted ring;
R 3 、R 4 、R 5 the same or different compounds are selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile, nitro, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 40 Alkyl radical, C 1 -C 40 Alkoxy radical, C 2 -C 40 Alkenyl radical, C 1 -C 40 Alkylthio radical, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 1 -C 40 Alkyl sulfoxide radical, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Arylthio, substituted or unsubstituted C 6 -C 60 Aryl sulfoxide radical, substituted or unsubstituted C 3 -C 40 Silyl, substituted or unsubstituted boron group, substituted or unsubstituted amine group, substituted or unsubstituted aryl phosphine group, substituted or unsubstituted phosphine oxide group, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups;
Ar 1 each independently selected from the group consisting of substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 A condensed ring aryl group, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups.
Preferably, the quinoxaline is selected from the group consisting of the following structures:
Figure BDA0003901831150000022
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each independently selected from hydrogen, deuterium, fluorineNitrile, methyl, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, triphenylene, carbazolyl, fluorenyl, dibenzofuran, or dibenzothiophene, R 1 And R 2 May be joined or fused to form a substituted or unsubstituted ring.
Preferably, R is 1 、R 2 Selected from hydrogen or phenyl; r 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each independently selected from hydrogen.
Preferably, each of said A independently represents CR 4 。
According to an embodiment of the invention, said a is CH.
Preferably, ar is 1 Selected from phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, pyrenyl,
Figure BDA0003901831150000032
A phenyl group, a peryleneyl group, a fluoranthenyl group, a tetracenyl group, a pentacenyl group, a benzopyrenyl group, a biphenyl group, an idophenyl group, a terphenyl group, a quaterphenyl group, a fluorenyl group, a spirobifluorenyl group, a phenanthrenyl group, a triphenylenyl group, a dihydropyrenyl group, a tetrahydropyrenyl group, a cis-or trans-indenofluorenyl group, a cis-or trans-indenocarbazolyl group, a cis-or trans-indolocarbazolyl group, a triindenylgroup, an isotridecylindenyl group, a spiroisotridecylindenyl group, a furanyl group, a benzofuranyl group, an isobenzofuranyl group, a dibenzofuranyl group, a thienyl group, a benzothiophenyl group, an isobenzothienyl group, a dibenzothienyl group, a pyrrolyl group, an indolyl group, an isoindolyl group, a carbazolyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, an acridinyl group, a phenanthridinyl group, a benzo [5,6, biphenyl 5363]Quinolyl, benzo [6,7]Quinolyl, benzo [7,8]Quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxaloimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthroixazolyl, isoxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthryl, benzopyrazinyl, pyrimidinylPyridyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazanthronyl, 2,7-diazpyrenyl, 2,3-diazpyrenyl, 1,6-diazpyrenyl, 1,8-diazpyrenyl, 4,5-diazpyrenyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorerynyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, carbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 3826 xzft 3826-oxadiazolyl, 3828-zxft 3428-oxadiazolyl, 5475-oxadiazolyl, 358625-oxadiazolyl, 3226-triazin-3296-3446-triazolyl, 3227-oxatift-328625-oxadiazolyl, 3296-7446-triazinyl, 3224-3446-tft-3296-triazolyl, quinoxalinyl, 328635-348696-oxadiazolyl, and combinations thereof.
Further, said Ar 1 Selected from the group consisting of groups represented by II-1 to II-17:
Figure BDA0003901831150000031
wherein,
Z 1 、Z 2 each independently selected from the group consisting of hydrogen, deuterium, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxy or carboxylate thereof, sulfonic or sulfonate thereof, phosphoric or phosphate thereof, C 1 -C 40 Alkyl radical, C 2 -C 40 Alkenyl radical, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 3 -C 40 Cycloalkenyl radical, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 An arylthioether group, or a substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups;
x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5;
t1 represents O, S, CR ' R ' or NAr ';
r 'and R' are each independently selected from hydrogen, deuterium, C 1 ～C 40 Alkyl group of (2), C1 to C 40 With heteroalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups, R 'and R' may optionally be joined or fused to form one or more additional substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or S in the formed rings; preferably, R', R "are methyl, phenyl or fluorenyl;
ar' is selected from C 1 ～C 40 Alkyl of (C) 1 ～C 40 Heteroalkyl of (a), C 3 ～C 40 Cycloalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups; preferably, ar' is methyl, ethyl, phenyl, biphenyl or naphthyl;
Figure BDA0003901831150000043
represents Ar 1 And L 1 The connecting bond of (1).
Preferably, in the above compound, L is 1 Selected from the group consisting of the following groups III-1 to III-15:
Figure BDA0003901831150000041
wherein,
Z 11 、Z 12 each independently selected from hydrogen, deuterium hydrogen, halogen atom, hydroxyl group, nitrile group and nitro groupAmino, amidino, hydrazine, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 40 Alkyl radical, C 2 -C 40 Alkenyl radical, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 3 -C 40 Cycloalkenyl radical, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 An arylthioether group, or a substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups;
Z 13 represents substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 An arylsulfonyl ether group, or a substituted or unsubstituted C 2 -C 60 One or more of a heterocyclic aryl group;
y1 represents an integer of 1 to 4; y2 represents an integer of 1 to 6; y3 represents an integer of 1 to 3; y4 represents an integer of 1 to 5;
T 2 represents a connecting bond, an oxygen atom or a sulfur atom;
“
Figure BDA0003901831150000044
"denotes with Ar 1 Or a linkage of a quinoxaline host structure.
The term "substituted or unsubstituted" as used herein means a group selected from the group consisting of hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitrile group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a carboxylate thereof, a sulfonic acid group or a sulfonate thereof, a phosphoric acid group or a phosphate thereof, and C 1 -C 60 Alkyl radical, C 2 -C 60 Alkenyl radical, C 2 -C 60 Alkynyl, C 1 -C 60 Alkoxy radical, C 3 -C 60 Cycloalkyl radical, C 3 -C 60 Cycloalkenyl radical, C 6 -C 60 Aryl radical, C 6 -C 60 Aryloxy radical, C 6 -C 60 An arylthioether group and C 2 -C 60 The heterocyclic aryl group may be substituted or unsubstituted with 1 or more substituents, or may be substituted or unsubstituted with substituents formed by connecting 2 or more substituents among the above-exemplified substituents.
Preferably, the quinoxaline derivative is selected from the group consisting of compounds represented by the following formula J475 to J600:
Figure BDA0003901831150000042
Figure BDA0003901831150000051
Figure BDA0003901831150000061
Figure BDA0003901831150000071
Figure BDA0003901831150000081
Figure BDA0003901831150000091
Figure BDA0003901831150000101
wherein-G-is selected from-O-or-S-;
*-T 3 is selected from-O-, -S-or one of the following structures:
Figure BDA0003901831150000111
* -and-represent a connecting bond.
The present invention also provides a method for preparing the quinoxaline derivative described above, as shown in scheme 1:
in the case of the scheme 1,
Figure BDA0003901831150000112
in scheme 1, the symbols used are as defined in formula (I) and Y is Cl, br, I or OTf;
the raw materials for synthesizing the compound shown in the formula (I) can be purchased from commercial sources, the method principle, the operation process, the conventional post treatment, the column purification, the recrystallization purification and other means are well known by the synthesizers in the field, and the synthesis process can be completely realized to obtain the target product.
Specifically, the compound of formula (I) is prepared by carrying out coupling substitution reaction on O-nitrile halogenated S0 and alkyne to prepare an intermediate S1; the intermediate S1 and nitromethane are subjected to ring closure to prepare an intermediate S2; carrying out reduction reaction on the S2 with the nitro group to prepare an intermediate S3 of o-diamino; intermediates S3 and R 1 R 2 The compound of the invention, formula (I), is prepared by condensation ring closure reaction of the ethyl diketone. Intermediate Ar 1 -L 1 -Y and its alkyne derivatives are prepared by palladium-catalyzed or base-catalyzed coupling reactions.
As palladium catalysts which may be used in the palladium-catalyzed coupling reaction, there may be selected: pd (P- t Bu 3 ) 2 、Pd(PPh 3 ) 4 、Pd 2 (dba) 3 、Pd 2 (dba) 3 CHCl 3 、PdCl 2 (PPh 3 ) 2 、PdCl 2 (CH 3 CN) 2 、Pd(OAc) 2 、Pd(acac) 2 、Pd/C、PdCl 2 、[Pd(allyl)Cl] 2 And the like, or a mixture of two or more thereof is used.
In addition, the base used in the palladium-catalyzed coupling reaction or base-catalyzed coupling reaction may be selected from: sodium tert-butoxide, potassium tert-butoxide, sodium hydride, lithium hydride, sodium tert-amylate, sodium ethoxide, sodium methoxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium, potassium hydride, triethylamine, cesium fluoride, and the like, and mixtures of one or two or more thereof.
The coupling reaction may be carried out in an organic solvent, wherein the organic solvent may be selected from: ether solvents such as diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, ethylene glycol ethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ether, diethylene glycol diethyl ether, or anisole, aromatic hydrocarbon solvents such as benzene, toluene, or xylene, chlorobenzene, dichlorobenzene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane, and one kind or a mixture of two or more kinds thereof can be used.
The invention also provides an organic electroluminescent material, the raw material of which comprises the quinoxaline derivative; an organic electroluminescent material comprising the quinoxaline derivative of the present invention has a carrier transporting ability.
The invention also provides application of the quinoxaline derivative in preparation of an organic electroluminescent element.
The present invention also provides an organic electroluminescent element comprising: the organic light-emitting diode comprises a first electrode, a second electrode, a sealing layer and more than one organic layer arranged between the first electrode and the second electrode; the material of at least one of the organic layer or the capping layer includes the quinoxaline derivative described above.
The organic electroluminescent element includes a cathode, an anode, and at least one light-emitting layer. In addition to these layers, it may also comprise further layers, for example in each case one or more hole-injecting layers, hole-transporting layers, hole-blocking layers, electron-transporting layers, electron-injecting layers, exciton-blocking layers, electron-blocking layers and/or charge-generating layers. An intermediate layer having, for example, exciton blocking function can likewise be introduced between the two light-emitting layers. However, it should be noted that each of these layers need not be present. The organic electroluminescent device described herein may include one light emitting layer, or it may include a plurality of light emitting layers. That is, a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. Particularly preferred are systems with three light-emitting layers, wherein the three layers can exhibit blue, green and red light emission. If more than one light-emitting layer is present, at least one of these layers comprises the quinoxaline derivative of the present invention according to the present invention.
Further, the organic electroluminescent element according to the invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, i.e. the light-emitting layer is directly adjacent to the electron blocking layer or hole transport layer or the anode and/or the light-emitting layer is directly adjacent to the electron transport layer or electron injection layer or the cathode.
In the other layers of the organic electroluminescent element according to the invention, in particular in the hole-injecting and hole-transporting layer and in the electron-injecting and electron-transporting layer, all materials can be used in the manner conventionally used according to the prior art. The person skilled in the art will thus be able to use all materials known for organic electroluminescent elements in combination with the light-emitting layer according to the invention without inventive effort.
Preference is furthermore given to organic electroluminescent elements in which one or more layers are applied by means of a sublimation process in which the temperature in a vacuum sublimation apparatus is below 10 -5 Pa, preferably less than 10 -6 Pa is applied by vapor deposition. However, the initial pressure may also be even lower, e.g. below 10 -7 Pa。
Preference is likewise given to organic electroluminescent elements in which one or more layers are applied by means of an organic vapor deposition method or by means of carrier gas sublimation, where 10 -5 The material is applied under a pressure between Pa and 1 Pa. A particular example of this method is the organic vapour jet printing method, in which the material is applied directly through a nozzle and is therefore structured.
Preference is furthermore given to organic electroluminescent elements in which one or more layers are produced from solution, for example by spin coating, or by means of any desired printing method, for example screen printing, flexographic printing, offset printing, photoinitiated thermal imaging, thermal transfer, ink-jet printing or nozzle printing. Soluble compounds, for example obtained by appropriate substitution. These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.
These methods are generally known to those skilled in the art, and they can apply them to an organic electroluminescent element comprising the compound according to the present invention without inventive work.
The invention therefore also relates to a method for producing an organic electroluminescent element according to the invention, at least one layer being applied by means of a sublimation method, and/or at least one layer being applied by means of an organic vapour deposition method or by means of carrier gas sublimation, and/or at least one layer being applied from solution by spin coating or by means of a printing method.
Furthermore, the present invention relates to quinoxaline derivatives comprising at least one of the invention indicated above. The same preferences as indicated above for the organic electroluminescent elements apply to the compounds according to the invention. In particular, other compounds may be preferably contained in addition to the quinoxaline derivative. The quinoxaline derivatives of the present invention are processed from the liquid phase, for example by spin coating or by printing processes, it being necessary to handle the preparation of the compounds of the present invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferred to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α -terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenetole, 3835-diisopropylbenzene, dibenzyl ether, triethylmethyl butyl glycol, triethylbutyl glycol, tripropyl glycol, diethylbutyl glycol, tripropyl glycol, or mixtures of these solvents.
Preferably, the organic layer includes a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, or an electron blocking layer.
The invention also provides a consumer product comprising the organic electroluminescent element.
In addition, unless otherwise specified, all starting materials for use in the present invention are commercially available, and any range recited herein includes any value between the endpoints and any subrange between the endpoints and any value between the endpoints or any subrange between the endpoints.
The invention has the following beneficial effects:
the quinoxaline derivative shown in the formula (I) provided by the invention has a condensed quinoxaline large plane structure, the thermal stability, the film-forming property and the carrier transporting capacity of molecules are greatly improved, and the compound is applied to an organic electroluminescent element, so that the driving voltage can be remarkably reduced, the luminous efficiency can be improved, and the service life can be prolonged.
Drawings
Fig. 1 shows a schematic diagram of an organic light emitting device 100. The illustrations are not necessarily drawn to scale. The device 100 may include a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, an emissive layer 106, a hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, a cathode 110, and a capping layer (CPL) 111. The device 100 may be fabricated by sequentially depositing the described layers.
Fig. 2 shows a schematic diagram of an organic light emitting device 200 with two light emitting layers. The device includes a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first light emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213. The device 200 may be prepared by sequentially depositing the described layers. Since the most common OLED devices have one light emitting layer, while device 200 has a first light emitting layer and a second light emitting layer, the light emitting peak shapes of the first light emitting layer and the second light emitting layer may be overlapping or cross-overlapping or non-overlapping. In the corresponding layers of the device 200, materials similar to those described with respect to the device 1 may be used. Fig. 2 provides one example of how some layers may be added from the structure of device 100.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the description of the present invention, "a plurality" means two or more unless otherwise specified; the terms "upper", "lower", and the like, indicate orientations or positional relationships that are based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and to simplify the description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. The experimental raw materials and the relevant equipment used in the following examples are commercially available unless otherwise specified, and the percentages are by mass unless otherwise specified.
The following examples are provided for testing the performance of OLED materials and devices using the following test apparatus and method:
OLED element performance detection conditions:
luminance and chromaticity coordinates: testing with a photosresearch PR-715 spectrum scanner;
current density and lighting voltage: testing using a digital source table Keithley 2420;
power efficiency: tested using NEWPORT 1931-C.
Example 1
A process for the preparation of compound J475, comprising the steps of:
the first step is as follows: preparation of intermediate Int-1
Figure BDA0003901831150000131
20.0mmol of 2-iodonaphthalene carbonitrile (prepared by the synthetic method reported in reference J.org.chem.,2013, 78, 2786-2791) was dissolved in 40mL of THF and 20mL of triethylamine under nitrogen, 22.0mmol of p-bromophenylacetylene, 2.0mmol of cuprous iodide, 0.2mmol of PdCl 2 (PPh3) 2 And (3) stirring the catalyst to react for 12 hours, filtering, concentrating the filtrate under reduced pressure, and separating and purifying by using a silica gel column to obtain an intermediate Int-1 with the yield of 91%.
The second step is that: preparation of intermediate Int-2
Figure BDA0003901831150000141
Under the protection of nitrogen, 50.0mmol of Int-1 is dissolved in 80mL of DMSO, 0.1mol of nitromethane and 0.1mol of potassium hydroxide are added, the temperature is raised to 110 ℃, the mixture is stirred and reacted for 1 hour, the temperature is reduced to room temperature, 150mL of saturated sodium bisulfite aqueous solution is added, the mixture is extracted by ethyl acetate, organic phase is dried, filtered, concentrated and dried under reduced pressure, and the mixture is separated and purified by an alumina column to obtain orange solid, and the yield is as follows: 87 percent.
The third step: preparation of intermediate Int-3
Figure BDA0003901831150000142
Under the protection of nitrogen, 20.0mmol of Int-2 is dissolved in 200mL of methanol, 1.0g of activated carbon and 0.74mmol of ferric chloride hexahydrate are added, the temperature is raised to reflux, 120.0mmol of 80% hydrazine hydrate solution is added dropwise, the mixture is stirred and reacted for 6 hours, the temperature is reduced to room temperature, the mixture is filtered, the filtrate is concentrated under reduced pressure to be dry, and brown solid is obtained without purification, and the yield is as follows: 98 percent.
The fourth step: preparation of intermediate Int-4
Figure BDA0003901831150000143
Under the protection of nitrogen, dissolving 20.0mmol of Int-3 in 200mL of glacial acetic acid, adding 21.0mmol of glyoxal hydrate, heating to reflux, stirring for reaction for 5 hours, cooling to room temperature, concentrating under reduced pressure to dryness, and separating and purifying by a silica gel column to obtain a white solid, wherein the yield is as follows: and 78 percent.
The fifth step: preparation of intermediate Int-5
Figure BDA0003901831150000144
Under the protection of nitrogen, dissolving 20.0mmol of Int-4 in 60mL of dry THF, cooling to-78 ℃ with liquid nitrogen, dropwise adding 22.0mmol of 2.5M N-butyllithium N-hexane solution, stirring for 10 minutes for reaction, dropwise adding 24.0mmol of triisopropyl borate, stirring for reaction for 1 hour, raising to room temperature, adding 20mL of 2N dilute hydrochloric acid aqueous solution, separating an organic phase, extracting an aqueous phase with ethyl acetate, drying the organic phase, filtering, concentrating the filtrate under reduced pressure to dryness, adding 50mL of petroleum ether for dispersion, filtering, washing a filter cake with petroleum ether to obtain a white solid, and obtaining the yield: 78 percent.
And a sixth step: preparation of Compound J475
Figure BDA0003901831150000145
Under the protection of nitrogen, 12.0mmol of intermediate Int-5, 10.0mmol of 2-chloro-4,6-diphenyl-1,3,5-triazine, 36.0mmol of anhydrous potassium carbonate and 40mL of toluene are mixed, 0.01mmol of Pd132 catalyst, 20mL of ethanol and 20mL of water are added, the mixture is heated to reflux and stirred for reaction for 12 hours, the mixture is cooled to room temperature, 50mL of water is added for dilution, dichloromethane is used for extraction, an organic phase is collected, dried and filtered, filtrate is decompressed and concentrated to dryness, and is separated by a silica gel columnPurification afforded compound J475 as a white solid in 76% yield, MS (MALDI-TOF): m/z =538.2045[ m ] +H] + ； 1 HNMR(δ、CDCl 3 )：9.18～9.16(2H，d)；8.99～8.97(1H，d)；8.93(1H，s)；8.78～8.74(4H，m)；8.62～8.58(2H，m)；8.33～8.30(2H，m)；7.96～7.85(4H，m)；7.61～7.57(1H，m)；7.55～7.51(4H，m)；7.45～7.41(2H，m)。
With reference to the above synthetic method, the following compounds shown in table 1 were prepared:
TABLE 1
Figure BDA0003901831150000151
Figure BDA0003901831150000161
Figure BDA0003901831150000171
Figure BDA0003901831150000181
Figure BDA0003901831150000191
Example 2
A method of making compound J597, comprising the steps of:
the first step is as follows: preparation of intermediate Int-6
Figure BDA0003901831150000192
Referring to the first step of the synthesis of example 1, SM-1 in the first step of example 1 was replaced with SM-2, p-bromophenylacetylene was replaced with trimethylsilylacetylene, and Int-6,G, an intermediate, was prepared as O, with a yield of 92%; g is S, yield 87%.
The second step is that: preparation of intermediate Int-7
Figure BDA0003901831150000193
Under the protection of nitrogen, dissolving 50.0mmol of Int-6 in 80mL of THF, cooling to 0 ℃, dropwise adding 10.0mL of 3N dilute hydrochloric acid solution, heating to room temperature, stirring and reacting for 1 hour, separating an organic phase, extracting an aqueous phase with ethyl acetate, drying the organic phase with anhydrous potassium carbonate, filtering, concentrating a filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain an intermediate Int-7, wherein the yield is as follows: 100 percent.
The third step: preparation of intermediate Int-8
Figure BDA0003901831150000194
Under the protection of nitrogen, 20.0mmol of Int-7 is dissolved in 50mL of DMF, 22.0mmol of 2-chloro-4,6-biphenylyl-1,3,5-triazine, 20.0mmol of potassium iodide, 2.0mmol of palladium acetate and 4.0mmol of DPPE are added, the temperature is raised to 90 ℃, the mixture is stirred and reacted for 12 hours, the temperature is reduced to the room temperature, the reaction solution is poured into 150mL of water, the filter cake is filtered, the filter cake is washed with water and ethanol, after the solid is dried, the solid is separated and purified by a silica gel column, and the intermediate Int-8,G is obtained as O, the yield is 75%; g is S, yield 77%.
The fourth step: preparation of intermediate Int-9
Figure BDA0003901831150000201
Referring to the synthesis of the second step of example 1, only Int-1 in the second step of example 1 was replaced with Int-8 to prepare intermediate Int-9,G as O or S with a yield of 84%.
The fifth step: preparation of intermediate Int-10
Figure BDA0003901831150000202
20.0mmol of Int-9 is dispersed in 200mL of methanol, 0.2g of 5% palladium/carbon is added, hydrogen is introduced at normal pressure, the reaction is carried out for 12 hours under stirring, the filtration is carried out, the filtrate is concentrated under reduced pressure and dried without purification, and a yellow-green solid is obtained with the yield: 100 percent.
And a sixth step: preparation of Compound J597
Figure BDA0003901831150000203
Referring to the fourth synthesis step of example 1, compound J597, G being O, white solid, yield 79%, MS (MALDI-TOF) was prepared by replacing Int-3 in the fourth step of example 1 with Int-10 only: m/z =604.2155[ m + H ]] + ； 1 HNMR(δ、CDCl 3 )：8.76～8.73(2H，d)；8.37～8.34(2H，m)；8.28(1H，s)；7.99～7.95(1H，m)；7.93(2H，s)；7.74～7.70(6H，m)；7.61～7.59(2H，m)；7.54～7.48(5H，m)；7.42～7.37(3H，m)；7.33～7.29(1H，m)。
With reference to the above synthetic method, the following compounds shown in table 2 were prepared:
TABLE 2
Figure BDA0003901831150000204
Figure BDA0003901831150000211
Figure BDA0003901831150000221
Figure BDA0003901831150000231
Wherein, T 3 Is selected from-O-, -S-orOne of the structures shown:
Figure BDA0003901831150000232
* -and-represent a connecting bond.
Example 3
An OLED element, as shown in fig. 1, the OLED element of this embodiment is a top emission light element, and includes a substrate 101, an anode layer 102 disposed on the substrate 101, a hole injection layer 103 disposed on the anode layer 102, a hole transport layer 104 disposed on the hole injection layer 103, an electron blocking layer 105 disposed on the hole transport layer 104, an organic light emitting layer 106 disposed on the electron blocking layer 105, a hole blocking layer 107 disposed on the organic light emitting layer 106, an electron transport layer 108 disposed on the hole blocking layer 107, an electron injection layer 109 disposed on the electron transport layer 108, and a cathode 110 disposed on the electron injection layer 109 and a capping layer 111 disposed on the cathode, and the method for manufacturing the OLED element without the hole blocking layer 107 includes the following steps:
1) The glass substrate coated with the ITO conductive layer is subjected to ultrasonic treatment in a cleaning agent for 30 minutes, washed in deionized water, subjected to ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baked to be completely dry in a clean environment, irradiated by an ultraviolet light cleaning machine for 10 minutes, and bombarded on the surface by a low-energy cation beam.
2) Placing the processed ITO glass substrate in a vacuum chamber, and vacuumizing to less than 1 × 10 -5 Pa, evaporating silver on the ITO film to form an anode layer with a thickness of
Figure BDA0003901831150000233
Continuing to respectively evaporate compounds HI01 and F4TCNQ as hole injection layers, wherein F4TCNQ is 3% of HI01 by mass, and the thickness of the evaporated film is
Figure BDA0003901831150000234
3) Continuously depositing a compound HTM101 on the hole injection layer to form a hole transport layer and depositing a film with a thickness of
Figure BDA0003901831150000235
4) Continuously depositing a compound EBL on the hole transport layer to form an electron blocking layer, wherein the thickness of the deposited layer is
Figure BDA0003901831150000236
5) Continuously depositing a compound H102 as a host material and GD10 as a doping material on the electron blocking layer, wherein GD10 is 3% of the mass of the formula H102, and the organic light-emitting layer is formed as an organic light-emitting layer of the device, and the thickness of the organic light-emitting layer obtained by deposition is set to be
Figure BDA0003901831150000237
6) Continuously evaporating a layer of LiQ and the compound formula (I) of the invention on the organic light-emitting layer as an electron transport layer of the element, wherein the compound formula (I) of the invention is 50% of the mass of the LiQ, and the thickness of the evaporated film is
Figure BDA0003901831150000238
7) Continuously evaporating a layer of LiF on the electron transport layer to form an electron injection layer, wherein the thickness of the evaporated film is
Figure BDA0003901831150000239
8) Evaporating a transparent cathode layer with magnesium and silver as elements on the electron injection layer, wherein the mass ratio of magnesium to silver is 1: 10, and the thickness of the evaporated film is
Figure BDA0003901831150000245
9) Evaporating a layer of NPD as a capping layer of the element on the transparent cathode layer, wherein the thickness of the evaporated film is
Figure BDA0003901831150000246
The OLED element provided by the invention is obtained.
The compound used in example 3 above has the following structure:
Figure BDA0003901831150000241
example 4
An organic electroluminescent device 200 is shown in FIG. 2 and comprises a substrate 201, an anode 202, and a hole injection layerLayer(s)203. A hole transport layer 204, a first light emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213.
Comparative example 1
Following the same procedure as in example 3, the compound of formula (I) in step 6) was replaced with ET01 to give comparative element 1;
Figure BDA0003901831150000242
comparative example 2
Following the same procedure as in example 3, the compound of formula (I) in step 6) was replaced with ET02 to give comparative element 2;
Figure BDA0003901831150000243
the organic electroluminescent element prepared by the above process was subjected to the following performance tests:
the driving voltage and current efficiency of the organic electroluminescent elements prepared in examples 3 and 4 and comparative examples 1 and 2 and the lifetime of the elements were measured using a digital source meter and a luminance meter. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent element reached 1000cd/m 2 The current voltage is the driving voltage, and the current density at the moment is measured; the ratio of the brightness to the current density is the current efficiency; the LT95% lifetime test is as follows: using a luminance meter at 1000cd/m 2 The luminance degradation of the organic electroluminescent element was measured to 950cd/m while maintaining a constant current at luminance 2 Time in units ofAnd (4) hours. The data listed in table 3 are relative data compared to comparative element 1.
TABLE 3
Figure BDA0003901831150000244
Figure BDA0003901831150000251
Figure BDA0003901831150000261
Figure BDA0003901831150000271
In the above table, me represents a methyl group, ph is a phenyl group, phPh is a biphenyl group, nap is a naphthyl group, and FR is 9,9-fluorenyl group.
As shown in table 3, the device prepared by the compound of the present invention has a lower driving voltage than ET01 under the same brightness, the current efficiency is improved significantly, which is up to 1.4 times that of the comparative device, and the LT95% lifetime of the device is greatly improved.
The compound ET01 in comparative example 1 is different from the compound of the present invention in that the planar conjugation ability of benzoquinoxaline is weak, resulting in high voltage and low efficiency. The compound is a large conjugated structure of naphthoquinoxaline or benzofuroquinoxaline or benzothiophene quinoxaline, has strong conjugation capability, has more excellent performances on molecular film formation and charge transmission, and more balanced charge transmission in an element, so that the element performance is remarkably improved.
The compound ET02 in comparative example 1 is different from the compound of the present invention in that although the planar conjugation ability of the benzophenazine is enhanced, the steric hindrance of the molecular plane is increased, and the molecular film formation and charge transport properties are reduced, resulting in high voltage and low efficiency. The compound of the invention increases the conjugated plane and reduces the steric hindrance, so the compound has more excellent performance on molecular film formation and charge transmission, and the charge transmission in the element is more balanced, thereby the element performance is obviously improved.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A quinoxaline derivative, characterized by having a structural formula as shown in formula (I):
Figure FDA0003901831140000011
wherein,
L 1 selected from the group consisting of single bonds, substituted or unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 Heteroarylene group;
X 1 、X 2 each independently is CR 3 Or X 1 And X 2 Represents a group of the following formula (II) or formula (III);
Figure FDA0003901831140000012
a represents, identically or differently on each occurrence, CR 4 Or N, and "^" indicates the adjacent group X in formula (I) 1 And X 2 ；
G represents O, S or NR 5 ；
R 1 、R 2 The same or different is selected from hydrogen or R 1 And R 2 Joined or fused to form a substituted or unsubstituted ring; and in X 1 And X 2 When is of the formula (II), R 1 、R 2 Is not hydrogen or phenyl;
R 3 、R 4 、R 5 the same or different is selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile group, nitro group, carboxyl group or carboxylate thereof, sulfonic group or sulfonate thereof, phosphoric group or phosphate thereof, C 1 -C 40 Alkyl radical, C 1 -C 40 Alkoxy radical, C 2 -C 40 Alkenyl radical, C 1 -C 40 Alkylthio radical, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 1 -C 40 Alkyl sulfoxide radical, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Arylthio, substituted or unsubstituted C 6 -C 60 Aryl sulfoxide group, substituted or unsubstituted C 3 -C 40 Silyl, substituted or unsubstituted boron group, substituted or unsubstituted amine group, substituted or unsubstituted aryl phosphine group, substituted or unsubstituted phosphine oxide group, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups;
Ar I each independently selected from the group consisting of substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups.
2. The quinoxaline derivative according to claim 1, wherein the quinoxaline is selected from the group consisting of the following structures:
Figure FDA0003901831140000021
R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 each independently selected from hydrogen, deuterium, fluorine, nitrile group, methyl group, phenyl group, biphenylyl group, terphenylyl group, naphthyl group, phenanthryl group, triphenylene groupGroup consisting of alkyl, carbazolyl, fluorenyl, dibenzofuranyl or dibenzothienyl, R 1 And R 2 May be joined or fused to form a substituted or unsubstituted ring.
3. The quinoxaline derivative according to claim 2, wherein R is 1 、R 2 Selected from hydrogen or phenyl; r 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each independently selected from hydrogen;
a independently of one another represents CR 4 ；
Ar 1 Selected from phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, pyrenyl,
Figure FDA0003901831140000031
A phenyl group, a perylene group, a fluoranthenyl group, a tetracenyl group, a pentacenyl group, a benzopyrenyl group, a biphenyl group, an idophenyl group, a terphenyl group, a quaterphenyl group, a fluorenyl group, a spirobifluorenyl group, a dihydrophenanthryl group, a triphenylene group, a dihydropyrenyl group, a tetrahydropyrenyl group, a cis-or trans-indenofluorenyl group, a cis-or trans-indenocarbazolyl group, a cis-or trans-indonocarbazolyl group, a trimeric indenyl group, an isotridecyl group, a spirotrimeric indenyl group, a spiroisotridecyl group, a furanyl group, a benzofuranyl group, an isobenzofuranyl group, a dibenzofuranyl group, a thienyl group, a benzothienyl group, an isobenzothienyl group, a dibenzothienyl group, a pyrrolyl group, an indolyl group, an isoindolyl group, a carbazolyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, an acridinyl group, a phenanthridinyl group, a benzo [5,6]Quinolyl, benzo [6,7]Quinolyl, benzo [7,8]Quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxaloimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthroixazolyl, isoxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthryl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazahnthryl, 2,7-diazepine, 2 zxft 8978-diazepine3-diazpyrenyl, 1,6-diazpyrenyl, 1,8-diazpyrenyl, 4,5-diazpyrenyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorrynyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, carbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 5749 zxf5749-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 58zzft 3552-triazinyl, 3575, these groups being derived from a benzoxalinyl, azaindolizinyl, benzoxalinyl, 3575, or a combination of these systems.
4. The quinoxaline derivative according to claim 1, wherein Ar is 1 Selected from the group consisting of groups represented by II-1 to II-17:
Figure FDA0003901831140000041
wherein,
Z 1 、Z 2 each independently selected from the group consisting of hydrogen, deuterium, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxy or carboxylate thereof, sulfonic or sulfonate thereof, phosphoric or phosphate thereof, C 1 -C 40 Alkyl radical, C 2 -C 40 Alkenyl radical, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 3 -C 40 Cycloalkenyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 An arylthioether group, or a substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups;
x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5;
T 1 represents O, S, CR 'R "or NAr';
r 'and R' are each independently selected from hydrogen, deuterium, C 1 ～C 40 Alkyl of (C) 1 ～C 40 Heteroalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups, R' and R "may optionally be joined or fused to form one or more additional substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or S in the formed rings; preferably, R', R "are methyl, phenyl or fluorenyl;
ar' is selected from C 1 ～C 40 Alkyl of (C) 1 ～C 40 Heteroalkyl group of (C) 3 ～C 40 Cycloalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups; preferably, ar' is methyl, ethyl, phenyl, biphenyl or naphthyl;
Figure FDA0003901831140000052
represents Ar 1 And L 1 The connecting bond of (1).
5. The quinoxaline derivative according to claim 1, wherein L is 1 Selected from a single bond or a group consisting of the following groups III-1 to III-15:
Figure FDA0003901831140000051
wherein,
Z 11 、Z 12 each independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitrile group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a carboxylate thereof, a sulfonic group or a sulfonate thereof, a phosphoric group or a phosphate thereof, C 1 -C 40 Alkyl radical, C 2 -C 40 Alkenyl radical, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 3 -C 40 Cycloalkenyl radical, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 An arylsulfonyl ether group, or a substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups;
Z 13 represents substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 An arylthioether group, or a substituted or unsubstituted C 2 -C 60 One or more of a heterocyclic aryl group;
y1 represents an integer of 1 to 4; y2 represents an integer of 1 to 6; y3 represents an integer of 1 to 3; y4 represents an integer of 1 to 5;
T 2 represents a connecting bond, an oxygen atom or a sulfur atom;
Figure FDA0003901831140000062
is represented by the formula Ar 1 Or a phenanthridine backbone.
6. The quinoxaline derivative according to any one of claims 1 to 5, selected from the group consisting of compounds represented by the following formulae J475 to J600:
Figure FDA0003901831140000061
Figure FDA0003901831140000071
Figure FDA0003901831140000081
Figure FDA0003901831140000091
Figure FDA0003901831140000101
Figure FDA0003901831140000111
Figure FDA0003901831140000121
wherein-G-is selected from-O-or-S-; * -T 3 Is selected from-O-, -S-or one of the following structures:
Figure FDA0003901831140000122
* -and-represent a connecting bond.
7. Use of the quinoxaline derivative according to any one of claims 1 to 6 for the preparation of an organic electroluminescent element.
8. An organic electroluminescent element, characterized by comprising: the organic light-emitting diode comprises a first electrode, a second electrode, a capping layer and more than one organic layer arranged between the first electrode and the second electrode; the material of at least one of the organic layer or the capping layer comprises the quinoxaline derivative according to any one of claims 1 to 6.
9. The organic electroluminescent element according to claim 8, wherein the organic layer comprises a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, or an electron blocking layer.
10. A consumer product comprising the organic electroluminescent element according to claim 8.
CN202211299144.2A 2022-10-21 2022-10-21 Quinoxaline derivative and application thereof Pending CN115677671A (en)

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